Esters of octyl alcohol with lower molecular weight sulpho carboxylic acids



duce surface tension and till ' BEST AVAILABLE COR C Acme mania R.arris,

poration ct n1 No lflii'awing.

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My invention relates to a new class of chemical substances, and more inparticular to a new class of chemical substances particularly adaptedfor use as detergents, wetting, penetrating, lathering, flotation andanti-spattering agents and for frothing purposes.

In certain classes of industries, there is a need for a. certain classof chemical substances usually used in relatively small quantities butcapable of use in larger quantities to secure an effect principally theresult of a wetting action such as at a water oil interface. In thetextile and dyeing industries, for example, there are many situationswhere a wetting or detergent action is imperative and many differentchemical substances have been produced calculated to repromote wettingin these industries. The 'use of prior art sub.- stances has not beenattended with unqualified success in all instances. In certain othertypes of industries, such as the margarine industries, for example,problems in preventing the spattering of margarine in problems areconsidered by some investigators as entirely a matter of wetting; inother words, by promoting greater attraction between the oleaginous andaqueous portions of the emulsion at the'interfaces thereof. Although theproblem is probably not one of wetting action entirely, it appears thatcertain compounds which in theory tend to concentrate at the water oilinterface will have an effect upon the spattering behavior of margarine.This problem is discussed and a remedy disclosed in my co-pendingapplication, Serial No. 566,156, filed September 30, 1931, now PatentNo. 1,917,256, as a continuation in part of a prior application, SerialNo. 475,622, now Patent No. 1,917,250.

The principal object of my present invention is the provision of a newclass of chemical substances capable of satisfactory use in connectionwith the problems hereinabove discussed.

Another object is the provision of a new class of chemical substanceswhich are in general of relatively simple structure and can be cheaplymade in commercial quantities.

Another object is the provision of a class of chemical substances of thecharacter set forth which in the main will toxic, even though employedin margarine.

Another object is the provision of a new class of chemical substanceshaving improved wetting characteristics.

Other objects and features of the invention Chicago, Hi, l The EmulsolCooration,

Application No. 627,096. Renewed of relatively ph roup which, fryinghave arisen. These be innocuous and non-v such foods as p w to @hicago,min a cor- July 30, 1932, run September 2%, 1938 will be apparent from aconsideration of the;

following detailed description. I

The substances of 'my invention are in general ester derivatives oflower molecular weight fatty. acids with at least one unesterifiedsulphonic acid group in the fatty acid radical wherein the groupesterified with the fatty acid has a lipophile radical with at leastfour carbon atoms. In certain circumstances there may be more than oneunesterifled sulphonic acid group in the fatg acid radical or there maybe sulphonic acid grou that are esterified and other sulphonic acidgroups that are notesterified, but in all cases there must be at leastone unesterified sulphonic .acid group in the fatty acid radical. Thefatty acid radical with the free sulphonic acid group is low molecularweight. Considering the compounds from another pect, the molecule ineach instance contains a relatively high molecular weight lipophilegroup and a relatively low molecular weight hydroin the class ofcompounds to which my present invention relates, are sulphonic acidradicals. From still another angle, the compounds may be considered ascombinations of a higher .molecular weight dipophile group and arelatively low molecular weight sulpho-fatty acid groups Amore completeunderstanding of what may comprise the lipophlle group andthe'particular character of the sulphofatty acid group will behad as thedetailed description progresses.

The function of the sulphonic acid group is to impart hydrophyllicproperties, that is, water wetting or water attracting properties, tothe molecule as a whole. The groups which are esterifled by thesulphonic fatty acid are in general of a lipophile character. At timesthey may be strongly lipophillic and at other times moderatelylipophillic. They may be of low molecular weight or of moderately highmolecular weight, depending upon the purpose for which the substancesmay be used. Furthermore, a group or groups which are esterlfied by thesulphonic fatty acid may have hydrophyllic radicals of their own. Anexample of this type of substance is monostearyl glycerol sulphoacetate,sodium salt.

It is evident that in the substance represented above, the group whichis esterified by the sulphuacetic acid happens to have a hydrophyllicradical 01' its own, namely the unesterifled hydroxy radical in theglycerol residue.

The lipophile groups entering into the molecular structure of mysubstances may be of simple character, as for example in cetylsulphoaoetate, or they may be of a more complex character as indicatedby the substance, the structural formula of which is written directlybelow.

Some additional examples oi. members of the.

group of substances which I have discovered are as follows:

Monolauryl glycerol sulpho-acetate (sodium nit) Cetyl ethyleneglycolsulpho-propionate (sodium salt) l CH1(GH:)1O( JCH: S 0

ONa

Octyl sulphoaeetate (sodium salt) Butyl diethyleneglyeol sulphoacetate(potassium salt) Monopalmityl glycerol sulpho-valerate (sodium salt)Monopelmityl 'ethyleneglycol sulphopmplonato (sodium salt) O NaMonolileyl disulphoacetyl glycerol (disodium salt) 0 Hfl-O--Gulln H1 0 0mo-o-i i-cnrs o Pslmityl tri-methylenc glycol sulphwacgtft: (sodiumsalt) 0 HaQ-O-E-Onfi i o H 0 0 0 H; 0 CH:80

' ONa a-stearyl, p-benzoyl, a sulphoocetyl g.yoerol (sodium salt) 0Ha-steeryl, fi-(p-sulphethoxy) benzoyl, a-sulphoproplonyl Qycerol a 4 gONs 011E10- O-CHr-CHr-O 0 I cuna-o-e-cm-s o /Ca o o cunro-l-cm-ho OCetyl sulphoacetate (calcium salt) stand that I may use many difl'erentexpedients for forming the compounds insofar as the dominant lipophilegroup and the relatively low moiii lecular weight sulpho-fatty acidgroup are concerned. In general, however, ester or ether linkages areutilized between these two portions of the compound, and the skilledchemist will understand in general the most approved practices insecuring this result. Numerous methods are also available for theintroduction of the sulphonic acid group. In the case of aromaticsulphonic acids, of course, standard sulphonation procedures employedfor producing aromatic sulphonic acids may be used, and, if desired, thelipophile group maybe introduced subsequently.

In the case of aliphatic sulphonic acids, and for that matter, even forthe production of arcmatic sulphonic acids, a reactive halogen may becaused to react with sodium sulphite or potassium sulphite or ammoniumsulphite or some other sulphite in aqueous solution, if desired.

Another method is to introduce a sulph-hydryl or disulphide or someother suitable sulphur containing group and then oxidize to thesulphonic acid with nitric acid or a permanganate or some otheroxidizing agent.

As an example of one of these methods, I describe herewith thepreparation of the sodium salt of cholesteryl sulphoacetate; nine partsof cholesterol, nine parts of brom acetyl bromide, and forty parts ofbenzene were heated under a reflux condenser for two hours at theboiling point of the mixture. The reaction mixture was then washedrepeatedly with hot water until it was substantially free of acid andfree of benzene by distilling from a steam bath. Seven parts oi thisreaction product were then treated with seven parts of sodium sulphite(NazSOa), dissolved in forty parts of hot water, for five hours at thetemperature of boiling water and with continuous, vigorousagitation.This reaction mixture was washed several times with hot brine until freeof sulphites, dried and finally purified by extracting the impuritieswith dry ethyl ether. Analysis showed that the product was the sodiumsalt of cholesteryl sulphoacetate in relatively pure. form, with anadmixture of sodium chloride.

Those skilled in the art are referred to my co-pending application,Serial No. 566,169, filed September 30, 1931, now Patent No. 1,917,260,in which I disclose the use of some of the compounds'of my presentinvention as anti-spattering agents for use in margarine. In thiscopending application I also treat of the manner of making some of thesecompounds.

Those of my substances which are uble in water may be recovered fromtheir solutions and from their water solutions in the customary mannerby concentrating and crystallizing. As stated hereinabove, as the massof the lipophile radical increases, solubility decreases and aflinityfor water is manifested by the dispersibility in water. From theseaqueous dispersions, my substances may be readily recovered by saltingout with suitable soluble electrolytes. Common salt is very satisfactoryfor this purpose in most cases. When salted out of an aqueous dispersionat temperatures ranging from 60 to 95 0., the substances are obtained inthe form of a paste with a water content ranging from approximately to75%. The more hydrophyllic the substance, the greater the water content,and, of course, the salt is present in the water of the paste inapproximately the same concentration in which it existed in thedispersion from which the paste was salted out.

Most of the compounds of my invention, although in many respectsdifierlng from each freely sol- I other in accordance with the numerousexamples given, nevertheless may be represented by the structuralformula wherein R is a lipophile group, X is the carbonhydrogen residueof the sulpho-fatty acid, Y is a cation and w is a small whole number,at least one.

I have previously referred to the fact that the lipophile group may initself contain hydrophile radicals, as, for example, in the case ofmonostearyl glycerol sulphoacetate, the hydroxy radical of the secondglycerine carbon has a recognized hydrophyllic character. The group as awhole, however, of which this hydroxy radical is a part, is dominantlylipophile, the single hydroxy radical in such a compound beinginsumcient to impart dominant hydrophile characteristics to the group asa whole. Moreover, in the case of a compound having an esterifiedsulphonic acid group, this sulphonic acid group will usually be found topossess a llpophile character or at least will not have a markedhydrophile character due to the additional group or radical which hasbeen attached to the sulphonic acid group by esterification. When thecharacter R is used in the formula, therefore, to represent a lipophilegroup, it is with the assumption that the group as a whole will notpossess a hydrophyllic character.

Considering more specifically the character of the llpophile group, itwill at once be apparent that for the most part I employ derivatives ofglycerols or glycols, although the lipophile group may comprise astraight chain higher molecular weight fatty acid group suitablyattached to the sulpho-fatty acid of relatively low molecular weight.Insofar as the sulpho-fatty acid group is concerned, I may employ asulphoacetate, sulpho butyrate, or other similar groups containing anunesterified sulphonic acid radical. In general, however, I have foundthat the sulphoacetates particularly produce compounds of exceptionallyvaluable characteristics and they have the advantage of being relativelyinexpensively produced from commercially available substances.

The term sulpho-fatty acid", as employed throughout the specificationand claims, is used in a strictly rigorous sense to mean an aliphaticcompound containing a sulphonic acid group. In other words, there is adirect carbon to sulphur linkage.

lldv present application is a continuation-inpart of my co-pendingapplication, Serial No. 481,349, filed September 11, 1930, now PatentNo. 1,917,255. Said co-pending application Serial No. 481,349 was acontinuation in part of my prior application Serial No. 475,622, filedAugust 15, 1930, now Patent No. 1,917,250.

What I claim is new and desire to protect b Letters Patent of the UnitedStates is: y

l. Octyl sulphoacetate.

2. An ester of a sulpho-carboxylic acid having from two to four carbonatoms with octyl alcohol.

3. An ester of octyl alcohol with a lower molecular weightsulpho-carboxylic acid, a sulphonic group of said lower molecular weightsulpholower molecular weight sulpho-carboxylic acid is connected.

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